Water-insoluble azo dyestuffs and fiber dyed therewith



Patented Nov. 17, 1936 UNl'lE g ATENT OFFICE WATER-INSOLUBLE AZODYESTUFFS AND FIBER DYED THEREWITH Karl Zahn, Kurt Schimmelschmidt, andHeinrich Koch, Frankfort-on-the-Main-Hochst,

Ger-

many, assignors to General Aniline Works, Inc., New York, N. Y., a.corporation of Delaware 12 Claims.

The present invention relates to new waterinsoluble azo dyestuffs and tofiber dyed therewith.

This application is a division of our copending application Serial No.590,782 filed February 3, 1932, which has matured into U. S. Patent No.1,936,926.

We have found that 2.20 dyestuffs of good fastness properties areobtainable by coupling a diazo-compound with a 2,3-hydroxynaphthoyl-4-amino-diphenyl containing a bridge in the 2,2- position of thediphenyl nucleus as, for instance, 2-aminofiuorene, 2-amino-fiuorenone,2-aminocarbazole or 2-amino-diphenylene-oxide, only such componentsbeing used which do not contain groups rendering the dyestuffs solublein water, as, for instance, a sulfonic acid or carboxylic acid group.The dyestufis may be produced in substance, on the fiber or in thepresence of any of the usual substrata which are adapted for theproduction of lakes.

Since derivatives of Z-aminofiuorene, 2-aminofluorenone etc., hitherto,have not been used for the preparation of dyestuffs of the said kind,the

fastness properties of the dyestufis obtained could not be foreseen.

With the aid of the azo-dyestuffs obtainable according to this inventionthere are obtained without complicated after-treatment, dyeings of greattinctorial power.

Many of the dyestuffs have brilliant tints which are very much in demandand they are, therefore, useful in industry as pigment dyes whenproduced in substance and as developing dyestuffs when produced on thefiber.

The new dyestufis are characterized by the following general formula:

' wherein R represents an aromatic radical, Y stands for hydrogen,alkoxy or halogen and X stands for a substituent of the group consistingof CH2, CO, NH and O. 1

The followingexamples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by weight, unlessotherwise stated:

(1) 1.5 grams of 2'.3'-hydroxynaphthoyl-2- aminofiuorene are dissolvedin 1.5 cc. of alcohol, 5

1.5 cc. of pyridine,

0.75 cc. of caustic soda solution of 34 B.

and

2.0 cc. of water, and

0.8 cc. of a formaldehyde solution of 30 per cent. strength is added.

The whole is allowed to stand for about halfan-hour and is thenintroduced into a solution of 20 cc. of Turkey red oil of per cent. 15

strength 20 cc. of caustic soda solution of 34 B., made up with water to1 liter.

50 grams of boiled cotton yarn are treated in this bath, the groundingliquor being taken up by the material to the extent of per cent. Bydeveloping the dyestufi with 1.5 grams of diazotized4-chloro-2-nitraniline, there is ob- 25 tained a vivid Bordeaux of goodfastness properties.

The dyestufi has the following formula:

' I OzN OH I CO-NH 35 (2) Into a diazo-solution prepared in the usualmanner from 16.8 parts of 4-nitro-2-aminoanisole, there is slowly run,while well stirring, a suspension of 38.6 parts of 2',3'-hydroxynaph- 40thoyl-Z-aminofluorene in a caustic soda solution to which there has beenadded the quantity of sodium acetate necessary for binding the excess ofmineral acid. After the formation of the dyestufi is completed, thesolution is filtered and 45 the solid matter is thoroughly washed. Thedyestuff may suitably be used in the form of a paste. When mixed withone of the usual substrata, a bluish red lake of good fastnessproperties is obtained. .59

(3) A paste is prepared from 2.5 grams of 2',3-hydroxynaphthoyl-2-aminofluorenone,

3 cc. of alcohol,

4 cc. of pyridine,

4 cc. of Turkey red oil of 50 per cent.

strength,

1.4 cc. of caustic soda solution of 34 B.,

1.2 cc. of formadlehyde and By using the same grounding liquor withoutfurther addition of 2',3'-hydroxynaphthoyl-2 aminofluorenone for asecond dyeing operation, there is obtained a dyeing equal to thatobtainable from a freshly prepared bath containing 1 gram of2,3'-hydroxynaphthoy1-2-aminofiuorenone.

Instead of the diazo-compounds used in the exam les, other diazo-,tetrazoor di z z 30 cc. of hot water; the paste is dissolved in p a a 0hot Water. compounds may be used.

2.5 cc. of caustic soda solution of 34 B. are The following tabledescnbes a number of added, and the Whole is made with binationsobtainable on the fiber according to the water to present invention:

1 liter.

Diazo component oupli g component Tint 4-nitro-2-amino-anisole 23-hydroxynaphthoyl-2- Bluish red.

aminofluorene. 3-nitro-4-arninoanisole Bordeaux. 4-0h1ol0-2aminnanisnlnBordeaux red. 4-chloro-3-nitraniline Bordeaux. 3-nitI0-4-aminofnlneneBordeaux red. 2, G-dichloranilina .d0 Yellowish red. 5l-amino-4-benzoylamino-2,5-dimethoxyb n n Redglish navy ue.4-amino-4-methoxy-diphenylamine. do- D ag: navy ue. 4-ch1oro-2-amino ne.d0 Scarlet red. l-amino-3-benzoylamino-4,G-dimethylb Yellowish red.l-aminoQA-dimethylb one Bluish red.1-amino-3-benzoylamino-4,fi-dimethoxyben one Dark violet.l-amino-4-benzoylamino-2-chloro-5-methoxybenmna Do.4-amino-2',3-dimethyl-azobenzene Garnet.4amino-4-nitro-2,5-dimethoxy-azob Black.

OCzHs ENQ- -Q Q- no. H30 1-aminonaphthalene Bordeaux red.2-aminonaphthalene .nn Red. 4-nitro-2-aminotoluene2,3-hydroxynaphthoyl-2- Yellowish red.

. aminofluorenone. 40 l-aminoi-bonzoylarnino-2-ch1oro-5-methoxyb emCurrant. 3-uitraniline- Orange. l-aminoanthraq on Bluish red.2,5-dinhlnraniline Ylellzowish-scare4-arm'no-2-nitro-3-rnethoxy-2,4-dimethylazobenzene Currant.4-amino-4-methoxy-diphenylamine Navy blue.1-amino-4-benzoy1amino-2,fi-diethoxyb one Do. 4-chloro-2-aminotohmnnYellowish-red. l-aminonaphthalene Bluish red. 2-aminonaphthaleneBrownish red. l-amino-2-methyl-5-chlorobenzene 2, 3 hydroxynaphthoylVivid medium 2-aininocarbazole. red. 4-amino-4-methoxy-diphenylamine d0Navy blue 4-nitro-2.5-dimethoxy-i-amino-azobenzene d0 lack.1-amino-2-methyl-4-nitrobenzens 2,3-hydroxynaphthoyl- Bluish red.

2 amino diphenylene oxide. l-aminoanthraq nne Do.l-amino-2-methyl-5-chlorobenzene Do.l-amino-2metl1y1-5-bromo-4-chlorobenzene Do.

50 grams of boiled cotton yarn are treated in Since an object 0f t p tnventi0n is to this bath, the grounding liquor being taken up ldyestuffs good- S S properties. by the material to the extent of percent By WhlCh dyestuffs are insoluble in Water and alkadeveloping thpdyestufi with 1 5 grams of diazm lies, it is to be understood that thearomatic 60 u nuclei of the general formulae appearing in the tized4-n1tro-2-am1no olu h r 1 am d vivid an i h r d 5 e S obt appendedclaims do not contaln any substituents y OW S e o goo ness prope 1ewhich are known to render organic compounds The dyestuffs the followmgformulasoluble in Water or alkalies and to tend to depreciate thefastness of the dyestuffs to alkalies. Substituents of this kind are,for instance, the sulfonic acid and the carboxylic acid group. H3O Weclaim: 1. The water-insoluble azo dyestufis of the following generalformula:

I N=N-R 00 OH X CO-NH- C0-NH wherein R represents an aromatic radical, Ystands for one of the group consisting of hydrogen, alkoxy and halogenand X stands for a substituent of the group consisting of CH2, CO, NHand O, yielding, when produced on the fiber, dyeings the shades of whichvary from orange to red to violet to blue to black and beingdistinguished by great tinctorial power, partially by a good fastness tolight.

2. The water-insoluble azo dyestufis of the following general formula:

wherein R represents a radical of the benzene series, Y stands for oneof the group consisting of hydrogen, alkoxy and halogen and X stands fora substituent of the group consisting of CH2, CO, NH and O, yielding,when produced on the fiber, dyeings the shades of which vary from orangeto red to violet to blue to black and being distinguished by greattinctorial power, partially by a good fastness to light.

3. The water-insoluble azo dyestufis of the following general formula:

wherein R represents a radical of the benzene series and X stands for asubstituent of the group consisting of CH2, CO, NH and O, yielding, whenproduced on the fiber, dyeings the shades of which vary from orange tored to violet to blue to black and being distinguished by greattinctorial power.

4. The water-insoluble azo dyestufi of the following formula:

OaN

yielding, when produced on the fiber, dyeings of a vived Bordeaux shadeof good fastness proper ties.

5. The water-insoluble azo dyestuff of the following formula: 5

yielding, when produced on the fiber, dyeings of a vived yellowish-redshade of good fastness properties.

6. The water-insoluble azo dyestufi of the fol- 20 lowing formula:

OCH:

KARL ZAHN. KURT SCHIMlWELSCHMIDT.

HEINRICH KOCH. 50

